Fluorinated epoxy resins containing polytetrafluoroalkylene fillers

ABSTRACT

Highly fluorinated polymers are synthesized and crosslinked to form fluorinated network polymers. These polymers are formed into paints by dissolving them into a solvent containing a pigment and extending the polymers with fluorinated fillers.

Elnited States Patent 260/77.5 AP, 618 D, 611 A, 37 EP, 328 EP, 31.2 R, 33.6 F, 830, 836, 837, 47 EP Field et a1. Mar. 18, 1975 FLUORINATED EPOXY RESINS [56] References Cited CONTAINING UNITED STATES PATENTS POLYTETRAFLUOROALKYLENE FILLERS 3,475,384 10/1969 Treschler 260/77.5 AP [75] inventors; Donald E. Field, Falls' Church, V; 3,489,813 1/1970 Dewhirst .1 260/2 EP James R. G iffith Riverdale 3,591,547 7/1971 Boudakin 260/77.5 AP Heights Md 3,706,772 12/1972 Reines 260/618 D 3,707,483 12/1972 Reincs 1 260/2 EP [73] Assignee: The United States of America as represented by the Secretary of the OTHER PUBLICATIONS Navy, Washington, DC. Lee & Neirlh, Handbook of Epoxy Resins, page l5-1 1 22 Filed: Aug. 22, 1973 and [21] Appl. No.: 390,673 Primary ExaminerM. J. Welsh Attorney, Agent, or FirmR. S. Sciascia; Arthur L. 52 U.S. c1 260/31.2 R, 117/1284, 117/161, Brannmg; ThOmaS McDonnell 260/2 BP, 260/2 EP, 260/32.8 EP, 260/33.6

F, 260/37 EP, 260/47 EP, 260/47 EN, [57] ABSTRACT 260/77.5 AP, 260/830, 260/836, 260/837, Highly fluorinated polymers are synthesized and cross- 1 260/611 260/618 D linked to form fluorinated network polymers. These [51] f C081; 30/14 Cosg 45/04 Cogg 51/02 polymers are formed into paints by dissolving them [58] held of Search 260/47 2 EP, 2 into a solvent containing apigment and extending the polymers with fluorinated fillers.

12 Claims, No Drawings FLUORINATED EPOXY RESINS CONTAINING or POLYTETRAFLUOROALKYLENE FILLERS CF3 3 BACKGROUND OF THE INVENTION a O The invention relates to epoxy resins and urethanes 5 l l useful as coatings, adhesives and laminates. These res- 3 ins have applications as automobile coatings, aircraft I windshield coatings,ship coatings, and spacecraft coat- RF an aliphatic fluorocarbon 2( ings. The polymers are highly hydrophobic and can be 2 Z beihgflh integer from 2 t0 l Both RF h used as coatings for automobiles which will greatly re- F y Occur the uhlt as tour Consecutive d h d fQr waxing times in their respective positions or R may be absent from the unit entirely. Hence .r is an integer from 1 to SUMMARY OF THE INVENTION 4 and y is an integer from O to 4. The prepolymers are Fluorinated polymers are produced by reacting one random copolymers SO that in each SUCCBSSiV unit X or more fluorinated diols with epichlorohydrin and 15 and y h a differeht number from the X and y in the NaOH. By this process copolymers of the polyol type previous unit and y will never be 0 throughout the forand the epoxy-terminated type are obtained, These (10- mula. it must also be pointed out that X Will seldom polymers are formed into paints by the addition of pigequal y.

ments, extenders and/or fillers. Highly hydrophobic The polyol prepolymer (2) is prepared by reacting paints are produced by using fluoropolymers as extendtwo fluorinated diols with epichlorohydrin. Generally, ers. the following reaction scheme is used to produce the prepolymer polyol:

(A) no p ('3 0H aoca (CF CH Ol-1 CF CF Z C\H 9HCH Cl m l R CH (lIl-ICH R CH ('IHCH 0 NaOH OH O (slight excess) x THE INVENTION The epox tClunuaLCu repolymer (l) is synthesized in a somewhat different manner than the polyol prepolymer (2). These prepolymers are synthesized via reaction (A) except that an excess epichlorohydrin is used to form terminal epoxy groups on the polymeric chain. These polymers are usually viscous liquids at room temperature since the chain length will be shorter than when a stoichiometric amount of epichlorohydrin is used.

Examples of polymers produced according to the invention via reaction A can be found in Ser. No. 373,322.

Paints can be made from the foregoing fluorinated The invention relates to the production of paints from polymers disclosed in our copending application Ser. No. 373,322 filed June 25, 1973, which is hereby incorporated byreference. In that application a new class of prepolymers was disclosed. The prepolymers 40 could be used as coatings or they could be crosslinked to provide further polymers. The prepolymer may be of low molecular weight wherein its terminal epoxy groups are significant or it may be of a higher molecular weight having such a great number of hydroxylgroups that the terminal epoxies are of little significance.

The former is a polymer comprising the formula:

. (1) cir paca a cn pacu 7 R ca caca ca qa ca 0 OH OH O we 1 is an integer less than 10. and then rhspensing by proper means in this solution The latter comprises units represented by the followsuitable pigments and extenders or fillers, Typical soling formula recurring more than nine times: vents are esters, i.e. butyl acetate and amyl acetate, ketones, i.e. methyl ethyl ketone and methyl isobutyl ke- (2) CH CHCH tone, and aromatic hydrocarbons, 1.e. xylene and tol- F 2 2 F Z? C Z yene. Paints have been defined as colored mixtures, X 0H usually liquids, with which suitable surfaces can be coated by brush or other means; the covering formed may be dull or lustrous and acts as a protective and pre- R may be either servative of the surface beneath it. The pigment, while CF3 7 usually an inorganic substance, may be a pure insoluble I organic dye, organic dye precipitated on an inorganic 0 C Q C 0 carrier or contain metals. The pigment extenders or fillcrs act to reduce the cost of the aim im rovc consis CF P p 3 3 tency, leveling, and pigment settling in the paint. Ccrpolymers by dissolving the polymers in suitable solvents taincxtcndcrs reinforce the structure ofthe dry coating brush. spray gun or roller. A catalyst such as metal mechanically, while other increase its resistance to the soaps, amines and other organometallics may he added transmission of moisture. The pigments and extenders also. are added to hide and/or protect the surface beneath In addition it has been found that the surface tension the paint. They often perform other important func- 5 of these polymers-is equal to or less than that of certain tions such as reflecting the destructive light rays. other fluoropolymers such as polytetratluoroethylenc Pigments useful in the present invention are titanium 11nd uorinzlted ethylene-propylene copolymer dioxide, phthalocyanine blue, carbon black and alu i- (FEP) which are manufactured in large volumes in pignum flake. Other pigment whi h may b d are th ment and extender partical size. This means that the white hiding pigments, such a b i carbonate whi It) foregoing prepolymers can be made into aint containlead, basic silicate white l d, b i lf hi l d ing FEP and TFE as pigment and/or extenders which zinc oxide,leaded zinc oxide,antimony oxide and lithoare Completely vetted the p p h' Powllclul pone. Extender igment a be ed a ll Among TFE and FEP can be added in a broad range of quantithese are the hydrated aluminum silicates, magnesium ties. TFE has been added from 0 to 75% by volume ili t (t l ili l i carbonate b i l. 15 The 70 volume percent loading of TFE in the fluorifate, calcium sulfate and powdered mica. Should color hated Vehicle had a yp Dlh'ometcr hardness of be desired the color pigments may be used. These are pp that y amount Short of 100 whims classified as natural pigments, synthetic inorganic pigpercent of the TFE and FEP extender could be added. ments and synthetic organic pigments. Thus, the paints contemplated are produced by dis- The natural pigments comprise the inorganic earth solving the prepolymer in a solvent. it is estimated that colors or mined products and a few organic materials at fias 35 eight percent solvent is required to proof vegetable and animal origin. Of chiefimportance are duce a flOWable SOhltiOh- Ah0Ve 65 Weight Perceht 1 the iron compounds, composed mainly of iron oxides Vent will Produce a Watery P Thus the 501M101) in combination with siliceous material and smaller perfOrmed ShOuld SiSt ro 35% I0 65 ol enthe centages of the oxides of manganese, aluminum, calamount of pigment required depends upon the hiding cium, and/or magnesium, together with some b power desired which in turn depends upon the particuceous matter. These ferro-ferric oxide pigments i lar use contemplated. The determination as to the clude the yellow ochers, the dark yellow siennas, the quantity of pigment is well within the skill of the art. brown umbers, the red hematites and burnt siennas, The crosslinking agent required is roughly stoichiometand the black magnetite or magnetic oxide. rically equal to that amount of polymer present. And as The synthetic inorganic pigments contemplated are stated above anything short of 100% FEP or TFE may the iron oxides, iron blues such as ferric-ferrocyanides, be used as a fluorinated polymeric extender. chromate pigments, chrome greens, chromium oxides To illustrate the production of paints from the prepolymers the following examples are presented in which the ingredients used are defined as follows:

and their hydrates. ultramarinc blue, and cadmium yellows and reds,

The synthetic organic pigments are the copper phthai v t s r locyanme blues and greens, toludine reds, para reds, Swen m l fi zkgz lithol reds. yellows, benzidine yellows, tungstated and ketonc t 60% b volume eth lenc lcol molybfllud plgnu'ms 4O monocthyl e ther (Exhale An important group of pigments are those used entirely for their ability to inhibit metallic corrosion. Polymer I These include red lead (Pb- 0 sublimed blue lead (basic lead sulfate, blue), calcium plumbate, basic lead i chromate, zinc chromate (zinc yellow), zinc tetroxy- H l chromate. and strontium chromate. Unique among the 5 rust-inhibiting pigments is a recently marketed basic 1 x y lead silico-chromate pigment consisting of a shell of basic lead chromate fused to an inert core of silica.

Metallic pigments for use in paints are usually in Polymer ll Polymer I wherein =0. flake form. A useful metallic pigment is aluminum. Me- Polymer III I v Cli filHCH R CH C\1HCH R CH CHCH CH C\H5Jl-l 0 0a 0a 0 v x tallic copper and its alloys with aluminum tin or zinc R,.-, R 1', x, y and 2, have the same definition as used yield a bronze finish. Zinc dust is useful as gold and silabove, 1 being equal to 3. ver flake and stainless steel flake.

The invention further contemplates the use of black EXAMPLE 1 pigments and fluorescent pigments. When the pigments and extenders are properly dispersed in solutions of the resins and compounded with crosslinlting agents such as Cerium p y y i such as toluene t gi 288 gm ofa 50/50 by weight solution of polymerl nate. hexamethylene dnsocyanate and derivatives 4 i i combination I;

1 0 gm microns); l 9 p y Such 15 dlethylene tlllhnmei a gm Titanium dioxide (0.2-0.4 microns); paint IS formed which can be applied to a surface by 30 gm phthalocyaninc blue 2 microns).

In a pebble mill were placed the following ingredi- This mixture was milled for 72 hours, removed from the mill and then stirred into it was the following:

Solvent combination I was added to achieve a spraying viscosity and applied to a suitable substrate. This paint when dry and hard was a medium blue color with a 60 angle gloss of 76%. After 4 months exposure at 45 south in Washington, DC. the reflectance was 73%.

EXAMPLE II The procedure of Example I was repeated in which polymer II was substituted for polymer I. 0.80 grams of carbon black was substituted for the phthalocyanine blue. When dry and hard this paint was light gray in color with 60 angle gloss of 86%. After 4 months exposure at 45 south in Washington, DC. the reflectance was 85%.

EXAMPLE III In a steel ball mill were placed:

200 gm of Polymer lll;

I00 gm Straotium Chromate pigment;

50 gm solvent combination I; and 50 gm resorcinol diglycidyl ether.

Milled for 48 hours, removed from mill and 30 gm di ethylene triamine were added. The paint was thinned for brush or spray application with solvent combination l. 'lhis paint makes an excellent primer to aluminum and aluminum alloys for fluorinated paint topcoats such as in Example I and II.

The novel paints can be produced and cured in situ without the use of heat. Due to their highly fluorinated nature and the ability to wet" TFE and FEP, the paints are highly hydrophobic and organophobic.

Obviously many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described.

What is claimed and desired to be secured by Letters Patent of the United States is:

l. A coating comprising a solution of an epoxy terminated polymer having recurring units of the formula in (RFCH2CHCH2-) (R CHZCHCHZ l X l V OH wherein the units recur more than 9 times, R is se 6 and CF3 er l l l l 3 a R is OCH (CF CH O, 2 being an integer from 2 to 12, is integer from I to 4 and y is an integer from 0 to 4, and a solvent in an amount from 35 to 65 weight percent of total composition;

said solution being mixed with a fluorinated polymeric extender, a pigment and a crosslinking agent.

2. A coating according to claim 1 wherein said crosslinking agent is selected from the group consisting of hexamethylene diisocyanate, toluene diisocyanate, and derivatives thereof.

3. A coating according to claim 1 wherein said polymeric extender is selected from the group consisting of polytetrafluoroethylene and fluorinated ethylenepropylene copolymer.

4. A coating according to claim 1 wherein the amount of crosslinking agent present is about stoichiometrically equivalent to the amount of polymer preseat.

5. A coating comprising a 50% by weight solution of an epoxy-terminated polymer of the formula I a ca c'zaca (RF ca wherein the unit recurs more than 9 times. R is selected from the group consisting of R is OCH (CF ),,CH O-, 2 being an integer from 2 to 12, x is an integer from 1 to 4 and y is an integer from 0 to 4, and a solvent;

said solution being mixed with a fluorinated polymeric extender selected from the group consisting of polytetrafluoroethylene and fluorinated ethylene-propylene copolymer, a pigment and a crosslinking agent. 6. A coating according to claim 5 wherein said cross linking agent is selected from the group consisting of hexamethylene diisocyanate, toluene diisocyanate and derivatives thereof and said crosslinking agent is present in a stoichiometric amount about equal to the amount of polymer present.

7. A coating comprising a solution of a polymer of the formula OH OH cn cucn (RFCH CH CHCH wherein R is selected from the group consisting of R is OCH (CF CH O, 2 being an integer from 2 to 12, i is an integer less than 10, x is an integer from 1 to 4 and y is an integer from 0 to 4, and a solvent in an amount from 35 to 65 weight percent of total composition; said solution being mixed with a pigment, a crosslinking agent and an extender.

8. A coating according to claim 7 wherein said cross linking agent is diethylene triamine.

- 9. A coating according to claim 7 wherein said polymeric extender is selected from the group consisting of polytetrafluoroethylene and fluorinated ethylenepropylene copolymer.

10. A coating composition according to claim 7 wherein the amount of crosslinking agent present is about stoichiometrically equivalent to the amount of polymer present.

1]. A coating comprising a by weight solution of a polymer of the formula CH CHCH CH CHCH I (R CH iIHCH 7 (RF cn cacn 2 wherein R is selected from the group consisting of CF CF I I 0 C I C O I I CF37 CF3 and C17 CF R is -OCH (CF Cl-l O,z being an integer from 2 to 12, i is an integer less than 10, x is an integer from 1 to 4 and y is an integer from 0 to 4, and a solvent;

said solution being mixed with a fluorinated polymeric extender selected from the group consisting of polytetrafluoroethylene and fluorinated ethylene-propylene copolymer, a pigment and a crosslinking agent.

12. A coating according to claim 11 wherein said crosslinking agent is diethylene triamine and is present in an amount about stoichiometrically equivalent to the amount of polymer present. 

1. A COATING COMPRISING A SOLUTION OF AN EPOXY - TERMINATED POLYMER HAVING RECURRING UNITS OF THE FORMULA
 2. A coating according to claim 1 wherein said crosslinking agent is selected from the group consisting of hexamethylene diisocyanate, toluene diisocyanate, and derivatives thereof.
 3. A coating according to claim 1 wherein said polymeric extender is selected from the group consisting of polytetrafluoroethylene and fluorinated ethylene-propylene copolymer.
 4. A coating according to claim 1 wherein the amount of crosslinking agent present is about stoichiometrically equivalent to the amount of polymer present.
 5. A coating comprising a 50% by weight solution of an epoxy-terminated polymer of the formula
 6. A coating according to claim 5 wherein said crosslinking agent is selected from the group consisting of hexamethylene diisocyanate, toluene diisocyanate and derivatives thereof and said crosslinking agent is present in a stoichiometric amount about equal to the amount of polymer present.
 7. A coating comprising a solution of a polymer of the formula
 8. A coating according to claim 7 wherein said crosslinking agent is diethylene triamine.
 9. A coating according to claim 7 wherein said polymeric extender is selected from the group consisting of polytetrafluoroethylene and fluorinated ethylene-propylene copolymer.
 10. A coating composition according to claim 7 wherein the amount of crosslinking agent present is about stoichiometrically equivalent to the amount of polymer present.
 11. A coating comprising a 50% by weight solution of a polymer of the formula
 12. A coating according to claim 11 wherein said crosslinking agent is diethylene triamine and is present in an amount about stoichiometrically equivalent to the amount of polymer present. 